CN100416908C - Manufacturing method of secondary battery - Google Patents
Manufacturing method of secondary battery Download PDFInfo
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- CN100416908C CN100416908C CNB2004100014157A CN200410001415A CN100416908C CN 100416908 C CN100416908 C CN 100416908C CN B2004100014157 A CNB2004100014157 A CN B2004100014157A CN 200410001415 A CN200410001415 A CN 200410001415A CN 100416908 C CN100416908 C CN 100416908C
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
Provided is a manufacturing method of a secondary battery. In the method of inspecting the secondary battery constituted of a positive electrode containing a lithium transition metal oxide capable of storing and discharging lithium ions, a negative electrode containing a carbon material capable of storing and discharging lithium ion, a separator consisting of an insulator separating the positive electrode and the negative electrode and an electrolyte containing lithium salt, a charging current value at constant-current charging in a charging process comprising a first constant-current charging after an assembly of the battery and following constant-voltage charging is set at 5 to 20 CmA, and an aging is carried out afterwards.
Description
Technical field
The present invention relates to a kind of manufacture method of secondary cell.More particularly, relate to a kind of easier and make the method for high-performance secondary cell with the short time.
Background technology
Consider from aspects such as economy,, use secondary cell mostly as the power supply of portable set.Secondary cell has polytype, and general the most universal is nickel-cadmium cell.In addition, Ni-MH battery is also popularized, but the lithium secondary battery of the high-energy-density higher than the output voltage of nickel-cadmium cell and Ni-MH battery becomes main flow in recent years.
But, in lithium secondary battery,, also require various function admirables such as cycle characteristics, load characteristic and temperature characterisitic except requiring to have the high-energy-density.In lithium secondary battery, after assembled battery, by primary charging (be called activation or chemical conversion), the part of lithium becomes positive pole, and positive pole is changed to new lithium compound (Li for example
xV
2O
5, Li
xMoS
2, Li
xTiS
2Or Li
xNbSe
3(x is different with the difference of each positive pole, is bigger than 3.0 little values than 0)), this mixture is worked as positive pole then.Along with the lithium that is contained in the positive pole moves to negative pole, the anodal composition (LiCoO for example that changes
2Li
xCiO
2, LiMn
2O
4Li
xMn
2O
4(x is different with the difference of each positive pole, is bigger than 3.0 little values than 0)), this mixture is worked as positive pole then.
Therefore as can be known, the characteristic of battery changes with the difference of charging method.Wherein, bigger to the influence of cycle characteristics, in order to improve this characteristic, a lot of technology are disclosed.
For example, make the density of charging current of back when charging for the first time by control, the method that improves cycle characteristics is disclosed (for example the spy opens flat 4-167374 communique, spy and opens that flat 11-26022 communique, spy are opened flat 11-297310 communique, the spy opens the 2001-110406 communique).
But, in these methods, because charging current is limited to 2mA/cm for the first time
2Below, so reach hundreds of cm for the charging area
2Practical battery, charging needs for a long time.
In addition, with 0.5mA/cm
2Above current density discharges and recharges repeatedly, and the method that improves cycle characteristics thus is disclosed (for example the spy opens the 2001-6671 communique).In addition, with 2mA/cm
2Above current density is charged, and the method that improves cycle characteristics and fail safe thus is disclosed (for example the spy opens flat 8-50921 communique).
But, in the method for above-mentioned these documents, need charge, and need to carry out repeatedly discharging and recharging more than 2 times at least with bigger electric current.Therefore, though cycle characteristics itself has improved,, need charge repeatedly and the equipment of the usefulness of discharging in order to make cell activation.In addition, these methods all are to be purpose to improve cycle characteristics and fail safe, but do not realize desired in recent years high-energy-density, multifrequency natures such as cycle characteristics, load characteristic and temperature characterisitic, thereby present situation is to fail to provide high performance battery.
In addition, as mentioned above, lithium secondary battery is compared with other batteries, and energy density is higher, but performance is easy to generate deviation, and owing to use the organic compound conduct in electrolyte, so worry that electrolyte can leak or break, the user is worked the mischief.In addition, when after assembling, charging for the first time,,, be easy to generate aberrations in property so the reaction in the battery is inhomogeneous because electrolyte does not also fully arrive each parts of battery.In addition, in the part that reaction is carried out superfluously, can cause that lithium separates out at the negative side skeleton that crystallization is separated out as resin-like.Separating out under the too much situation, this crystallization breaks through the division board (separator) that hides positive pole and negative pole and contacts with positive pole, causes micro-short circuit (micro-short), makes the voltage difference of terminal voltage become big, and then may cause heating and overheated.
Therefore, usually in the assembling procedure of lithium secondary battery, after assembling, place certain hour, fully arrive the each several part of battery, carry out the first time then and charge up to electrolyte.By the detection of lithium secondary battery, in the fabrication stage of lithium secondary battery, must pick out bad battery as far as possible, the detection in the operation of particularly charging for the first time is very important.
Open in the 2001-228224 communique the spy, disclose such method, promptly after the charging first time after assembling, carry out the Ageing Treatment in a week, discern because the bad battery that micro-short circuit causes according to the terminal potential difference before and after the Ageing Treatment.In addition, open in the 2000-28690 communique the spy, disclose such method, the charging first time after promptly using Weak current to assemble then according to the potential decay curve of battery, is discerned the bad battery that causes owing to short circuit.
Utilize said method,, exist Ageing Treatment chronic, and need be used to make the problem of the charging process of cell activation in addition though the battery of stay in grade can be provided.
Summary of the invention
The present invention proposes in view of the above problems, by providing a kind of easy, easy and make secondary cell activation at short notice, and judge that it is bad, obtain the secondary cell manufacture method of the good secondary cell of cycle characteristics, load characteristic and temperature characterisitic, can address the above problem.
According to the present invention, a kind of manufacture method of secondary cell is provided, it is characterized in that, secondary cell for assembling, above-mentioned secondary cell is by constituting with the lower part: positive pole comprises and can absorb the lithium transition-metal oxide of emitting lithium ion; Negative pole comprises and can absorb the material with carbon element of emitting lithium ion; Division board is separated above-mentioned positive pole and negative pole, is made of megohmite insulant; And the electrolyte that comprises lithium salts, after secondary cell for assembling, carry out the constant current charge of 5～20CmA, when reaching 4～4.3V, terminal voltage carries out constant-potential charge with this voltage, finished the operation of charging for the first time in 3～30 minutes later on, and the current value of the battery when measuring above-mentioned constant-potential charge and/or the temperature of the battery in the charging operation, judge the bad of battery, after the operation of charging for the first time, carry out the timeliness operation, then, carry out the constant current charge of 0.2CmA, carry out constant-potential charge with this voltage when terminal voltage reaches 4.2V, finish the operation of charging for the second time when current value reaches 0.05CmA.
According to the present invention, a kind of manufacture method of secondary cell is provided, it is characterized in that, secondary cell for assembling, above-mentioned secondary cell is by constituting with the lower part: positive pole comprises and can absorb the lithium transition-metal oxide of emitting lithium ion; Negative pole comprises and can absorb the material with carbon element of emitting lithium ion; Division board is separated above-mentioned positive pole and negative pole, is made of megohmite insulant; And the electrolyte that comprises lithium salts, after secondary cell for assembling, carry out the constant current charge of 5～20CmA, when reaching 4～4.3V, terminal voltage carries out constant-potential charge with this voltage, finished the operation of charging for the first time in 3～30 minutes later on, after the operation of charging for the first time, carry out the timeliness operation, and by being determined at the magnitude of voltage that carries out the battery in the timeliness operation, judge the bad of battery, then, carry out the constant current charge of 0.2CmA, carry out constant-potential charge with this voltage when terminal voltage reaches 4.2V, finish the operation of charging for the second time when current value reaches 0.05CmA.
Manufacture method according to secondary cell of the present invention, by after the assembled battery the first time constant current charge and the charging operation that constitutes of constant-potential charge subsequently in, charging current value in the constant current charge is set at 5～20CmA, carry out Ageing Treatment then, so battery can not damage, can not generate heat yet, thereby can improve load characteristic, temperature characterisitic and cycle characteristics owing to big electric current makes battery itself.And, do not need to be used to make the special manufacturing equipment of this high performance secondary cell, thus can be easy, easy and make, and then can improve rate of finished products at short notice, reduce manufacturing cost, the secondary cell that manufacturing price is cheap.Particularly, carrying out in the time below 120 hours more than 2 hours under the situation of Ageing Treatment, the polarization of inside battery relaxes and can fully carry out, thereby can carry out Ageing Treatment efficiently.
In addition, in the manufacture method of secondary cell of the present invention, (1) in the temperature of passing through to measure the battery in the current value of the battery in the constant-potential charge and/or the operation of charging, judge under the condition of poor of battery, charging during with charging current value about existing 0.1CmA is compared, can in the very short time, charge, therefore can utilize rapid and easy method to carry out the bad judgement of battery.Therefore, do not need special manufacturing installation, checkout gear etc., can realize the reduction of manufacturing cost, thereby well behaved secondary cell can be provided with cheap price.
In addition, in the manufacture method of secondary cell of the present invention, (2) by measuring the magnitude of voltage of battery, are judged under the condition of poor of battery in the timeliness operation, can carry out the bad judgement of battery with easy method, thereby well behaved secondary cell can be provided with cheap price.
In addition, the bad judgement of battery is carried out in above-mentioned by making up (1) and (2), high accuracy and judge the bad of battery reliably more, thus can obtain high performance secondary cell.
Description of drawings
Fig. 1 is that the manufacture method that is illustrated in secondary cell of the present invention is applied under the situation of normal battery, the current potential and the time dependent figure of electric current of the battery in the operation of charging for the first time.
Fig. 2 is illustrated in the battery that internal short-circuit has taken place, the time dependent figure of electric current of the battery in the operation of charging for the first time.
Fig. 3 is that the manufacture method that is illustrated in secondary cell of the present invention is applied under the situation of normal battery, the time dependent figure of surface temperature of the battery in the operation of charging for the first time.
Fig. 4 is illustrated in the battery that internal short-circuit has taken place, the time dependent figure of surface temperature of the battery in the operation of charging for the first time.
Fig. 5 is that the manufacture method that is illustrated in secondary cell of the present invention is applied under the situation of normal battery and the battery that internal short-circuit has taken place the time dependent figure of open voltage of the battery in the timeliness operation.
Fig. 6 is illustrated in existing method is applied under the situation of normal battery, the time dependent figure of electric current of the battery in the operation of charging for the first time.
Embodiment
(first execution mode)
The manufacture method of the secondary cell of first embodiment of the invention is chiefly directed to after the secondary cell for assembling, and the operation of charging is carried out the timeliness operation then.
The charging operation is after secondary cell for assembling, carry out the charging first time in order to make cell activation, as this charging process, as shown in Figure 1, charge with certain current value, till arriving certain current potential (A among Fig. 1), after arriving the free voltage of setting, make current attenuation (B among Fig. 1) with the certain voltage that is not more than this current potential, carry out so-called constant current (A)-constant voltage (B) charging.Charging for the first time needn't be carried out full charging with respect to battery capacity, gets final product complete charge as long as charge to suitable charge volume.
Consider and do not destroy battery, do not make battery itself heating and further improve the aspects such as cycle characteristics of the secondary cell that is obtained, the preferred 5～20CmA of the current value during constant current charge.Wherein, 1CmA represents to make within a certain period of time the battery capacity needed current value that discharges.For example, if capacity is the battery of 1500mAh, then 1500mA is equivalent to 1CmA, and for this battery, 5CmA is 7500mA.
From the size of primary charge volume, prevent that the electrolytical redox aspect of battery from considering, as described later, for example using LiCoO
2, LiNiO
2Or LiMn
2O
4Under the situation as the secondary cell of positive active material, the charging potential during constant-potential charge is preferably about 4.0～4.3V.The control of the charge volume in the charging operation can be limited by the charging interval, also can be limited by charging capacity.Charging interval was preferably about 3～30 minutes.Charging capacity be preferably battery rated capacity about 30～70%.In the method for the invention, charging capacity is different with the difference of current value, but because the current value at charging initial stage is bigger, so within about 30 minutes, can carry out 70～90% chargings of rated capacity.
During the charging operation, though needn't heat, cool off battery especially, but when judging that battery is bad, because excessive variations in temperature can make potential measurement produce error in temperature that worry is high or extremely low temperature or the keeping, so should in a certain temperature range, charge, the scope below arbitrary temp ± 5 ℃ for example, as the scope below 10 ℃, the scope of preferred room temperature ± below 5 ℃.In addition, this charging operation can not placed the stipulated time with battery after assembled battery, and carries out at once after assembling.In addition, preferred only utilize once constant current charge and only once constant-potential charge carry out this charging operation.
After the operation of charging for the first time, carry out timeliness (ageing) operation.The timeliness operation is not carried out operations such as charge or discharge to battery, place and carry out but be in open state by the terminal that makes battery.The time of timeliness operation does not limit especially, but considers fully carrying out that the polarization of inside battery relaxes, and is preferred more than about 2 hours.In addition, consider the increase of production efficiency, item for disposal etc., preferred below about 120 hours.Battery after the timeliness operation can charge, and also can discharge.During the timeliness operation, needn't especially battery be heated or cool off, but when judging battery bad, because excessive variations in temperature can make potential measurement produce error in temperature that worry is high or extremely low temperature or the keeping, so should in a certain temperature range, carry out the timeliness operation, the scope below arbitrary temp ± 5 ℃ for example, as the scope below 10 ℃, the scope of preferred room temperature ± below 5 ℃.
Be applicable to preferably above-mentioned lithium secondary battery, the lithium rechargeable battery of secondary cell of secondary cell manufacture method of the present invention.Under the various conditions shown in the table 1, the secondary cell that is obtained is carried out carrying out Ageing Treatment after the first time charging.Ageing Treatment is to make the terminal of battery open, places official hour under 25 ℃ environment.
Then, after the 0.2CmA constant current charge, carry out the constant-potential charge of 4.2V, reach moment of 0.05CmA at current value, charging finishes.After charging finishes, under the following conditions the characteristic of battery is estimated.Other characteristics except temperature characterisitic all are to measure under 25 ℃ environment.
Load characteristic=(discharge capacity under the discharge capacity/0.2CmA under the 1CmA) * 100 (%)
Temperature characterisitic=(discharge capacity under the discharge capacity/25 ℃ environment under 10 ℃ of environment under the 1CmA under the 1CmA) * 100 (%)
Cycle characteristics=(capacity of the 1st circulation under the capacity/1CmA of the 300th circulation under the 1CmA) * 100 (%)
The result who is obtained has been shown in the table 1.
(table 1)
*: when reaching 0.05CmA, finishes current value
According to the result of table 1, any one compares embodiment 1～4 with the comparative example 1 that charges with low current, and any one characteristic in its load characteristic, temperature characterisitic, the cycle characteristics all improves.In addition, can judge any one characteristic poor than the battery of comparative example 1 all of the battery of comparative example 2～9.
(second execution mode)
Below, the manufacture method of the secondary cell of second embodiment of the invention is described.
The manufacture method of the secondary cell of second execution mode is to charge for the first time after secondary cell for assembling in the operation, the current value when measuring constant-potential charge and/or the temperature of the battery in the charging operation, and judge that in manufacturing process battery is bad.
Under the situation of this manufacture method, consider easily that the decay of the current value after the constant current charge that detects in the charging for the first time is unusual, be accompanied by excessive heating that current value increases and electrolytical deterioration equivalent damage etc., current value is set at 5～20CmA.Like this, be set at 5～20CmA and charge, can in the very short time, finish constant current charge with bigger current value by the current value in the constant current charge for the first time.And can confirm that even charge with so bigger current value, performance can deterioration yet, and can activate fully.
Therefore, in above-mentioned scope, carry out constant current charge, only by measuring the current value of the battery in the constant-potential charge, just can under this current value situation different, judge that this battery is bad then with situation shown in Figure 1.For example, under the situation that inside battery is short-circuited, as shown in Figure 2, can observe the phenomenon that electric current rises suddenly.Therefore, the value of differential is carried out in the decay of the current attenuation amount current value of the unit interval when calculating with the time constant-potential charge, when this value is timing, can judge the phenomenon that electric current rises has taken place, thereby can judge that battery is bad.In addition, not only under the situation that current value sharply rises, and confirming situation that situation, rising and decline that current value slowly rises alternately take place, sharply descend under the situation of degradation, can infer that also that certain takes place is unusual, thereby the judgement battery is being bad.In addition, this current value preferably changes and METHOD FOR CONTINUOUS DETERMINATION in time, but also can be so that the time interval is measured arbitrarily.In addition, during the charging operation, though needn't heat, cool off battery especially, but when judging that battery is bad, owing to worry that excessive variations in temperature can make potential measurement produce error in high temperature or extremely low temperature or the keeping, so should in a certain temperature range, charge the scope below arbitrary temp ± 5 ℃ for example, as the scope below 10 ℃, the scope of preferred room temperature ± below 5 ℃.
(the 3rd execution mode)
The manufacture method of the secondary cell of the 3rd execution mode is a temperature of measuring the battery surface in the charging operation, under its situation different with temperature shown in Figure 3, judge battery very/bad.That is, usually as shown in Figure 3, under the situation of carrying out the charging first time, the temperature of battery rises after the charging beginning at once, after official hour, reaches maximum temperature afterwards in for example about 1 minute, and the temperature of battery slowly descends then.Under the situation that inside battery is short-circuited, for example shown in Figure 4, can observe the phenomenon that the temperature of the battery surface of temporary transient decline rises suddenly.Therefore, the increase and decrease amount of the battery surface temperature of unit interval when measuring charging is after the charging beginning, initial temperature rises normal, the temperature increase and decrease amount of unit interval is under the positive situation, can judge that this battery has taken place unusually, thereby judge that it is bad for the second time.In addition, the situation that the surface temperature of the battery in the operation becomes in for the second time later temperature rises more than the temperature of regulation of preferably will charging is judged as bad.As the temperature of regulation, can for for example about 40 ℃, about about 45 ℃, 50 ℃ or about 60 ℃.In that having taken place, primary temperature the rise situation, the temperature that do not take place in suitable scope, suitable period of too violent situation (for example high situation about 10 ℃ or more than common temperature), primary temperature that rise descend violent situation, rising and decline alternately under the unusual situation of situation, the impedance of generation, can infer that impedance has taken place waits certain unusual unusually, thereby judge that it is bad.In addition, the temperature of this battery preferably changes in time and measures continuously, but also can be so that the time interval is measured arbitrarily.In addition, the temperature during the charging operation and above-mentioned same is preferably in a certain temperature range.
(the 4th execution mode)
The manufacture method of the secondary cell of four embodiment of the invention is by measuring the magnitude of voltage of the battery in the charging operation timeliness operation afterwards, judging the bad of battery.Under the situation that inside battery is short-circuited, the change in voltage of unit interval is than the big of internal short-circuit do not taken place.In the present invention, in the operation of charging for the first time, owing to flow through the above big electric current of 5CmA in the battery, so the polarization in the battery must become greatly, the current potential after charging finishes descends and also becomes big, thereby can easily judge the bad of battery.That is, usually as shown in Figure 5, the phenomenon that current potential descends taking place, but under the situation that inside battery is short-circuited, shown in the B among Fig. 5, the big phenomenon of degree change that current potential descends takes place.Therefore, the degree that current potential in stipulated time after Ageing Treatment begins descends become reduction that the current potential of setting when following, unit interval descends become setting when above, current potential descend when not carrying out smoothly, when current potential rises, can infer that certain has taken place is unusual, thereby judge that it is bad.The time of Ageing Treatment does not limit especially, but considers and be easy to detect the bad of battery, should be more than 20 minutes, and is preferred more than 30 minutes.In addition, the current potential in this Ageing Treatment descends preferably variation in time and measures continuously, but also can be so that the time interval is measured arbitrarily.In addition, the temperature during the Ageing Treatment and above-mentioned same is preferably in a certain temperature range.
(the 5th execution mode)
The manufacture method of the secondary cell of the 5th execution mode of the present invention is that the mensuration of above-mentioned current value, the mensuration of temperature, the mensuration of magnitude of voltage are carried out in combination.Specifically, can enumerate the combination of the mensuration of the mensuration of the mensuration of mensuration, current value of the mensuration of mensuration, temperature of the mensuration of mensuration, current value of the mensuration of current value and temperature and magnitude of voltage and magnitude of voltage and temperature and magnitude of voltage.By such combination, can judge the bad of battery more accurately.
Below the manufacture method of secondary cell of the present invention is elaborated.
At first, make lithium secondary battery according to following order.
Use cobalt acid lithium LiCoO
2As positive active material.LiCoO
2Synthesize with known method.Use from the CuK ray of the 2kW of the inclosure pipe of target Cu output as x-ray source, to synthetic LiCoO
2Carry out X-ray diffraction and measure, utilize iodometry to carry out the valence mumber analysis of cobalt and utilize ICP to carry out elementary analysis, be confirmed to be LiCoO thus
2
With mortar the above-mentioned positive active material that obtains is pulverized, will be mixed with it as the acetylene black of about 10wt% of conductive agent with as teflon (registered trade mark) toner of about 10wt% of binding agent then.This mixture is dissolved in the solvent of N-N-methyl-2-2-pyrrolidone N-etc., makes it become pulpous state, utilize scraper plate (doctor blade) method that it is coated on two surfaces of aluminium foil then, suppress after dry, make anodal.
Use the native graphite powder as negative electrode active material.To mix with this native graphite powder as teflon (registered trade mark) toner of about 10wt% of binding agent.This mixture is dissolved in N-N-methyl-2-2-pyrrolidone N-equal solvent, makes it become pulpous state, then it is coated on two surfaces of Copper Foil, suppress after the drying, make negative pole.
Between positive pole of making as mentioned above and negative pole, insert the division board of porous matter polyethylene system, twine electrode and insert metallic container afterwards, it is immersed as the electrolytical LiPF that dissolves 1 mol
6The carbon ester ethene of 50 volume % and the diethyl carbonate of 50 volume %.Then, the peristome of canister is sealed, finished the manufacturing of secondary cell with resin cap.This battery is called battery A.
In addition,, be manufactured on the battery that scatters the aluminium powder 1mg of 200 meshes (mesh) between division board and the electrode, the battery of internal short-circuit has taken place as simulation in order to compare.This battery is called battery B.
In addition, in order to compare, make except making the LiPF of 0.1 mol
6Be dissolved in outside the electrolyte, with the same battery of battery A, as the battery that high impedance status has taken place.This battery is called battery C.
Use each 3 of battery A, battery B, battery C respectively, measure on one side battery current potential, flow through the surface temperature of the current value and the battery of battery, charge Yi Bian under 25 ℃ environment, carry out the first time.According to the battery capacity of calculating by the weight of the electrode active material of these batteries, carry out the 10CmA constant current charge down in 90 seconds, switching on flows through electric current, so that the charging potential under the constant voltage is 4.2V.In addition, complete charge after charging beginning 15 minutes, then at room temperature 24 hours, measure open voltage on one side, carry out Ageing Treatment on one side.Table 2 shows its result.
(table 2)
Compare with normal battery A, among the battery B 2 the constant-potential charge processes in charging for the first time, should change in time originally decay electric current at a time sharply rise.In addition as can be seen, all battery C compare with battery A, and the decay of current value is violent, and temperature rises also change greatly.Can see that in addition the normal battery current potential in the timeliness operation that charges the first time among the battery B also reduces.
According to this result as can be known, utilize detection method of the present invention, can detect bad battery reliably.
In addition, each 3 for battery A, battery B, battery C are carried out the charging first time, promptly carry out 4 hours 0.2CmA constant current charge, carry out the constant-potential charge of 4.2V then, reach the moment of 0.05CmA up to current value, complete charge then is except carrying out this charging, with above-mentioned same.Fig. 6 and table 3 show its result.
(table 3)
According to Fig. 6 as can be known, only among the battery B that current attenuation has taken place is unusual, among the battery B other 2 normal.In addition, utilize this method, fail to detect the unusual of battery C.
Comparison sheet 1 and table 2 utilize the detection method of secondary cell of the present invention as can be known, and bad battery can judge rightly.
Claims (9)
1. the manufacture method of a secondary cell is characterized in that,
Secondary cell for assembling, above-mentioned secondary cell is by constituting with the lower part: positive pole comprises and can absorb the lithium transition-metal oxide of emitting lithium ion; Negative pole comprises and can absorb the material with carbon element of emitting lithium ion; Division board is separated above-mentioned positive pole and negative pole, is made of megohmite insulant; And the electrolyte that comprises lithium salts,
After secondary cell for assembling, carry out the constant current charge of 5～20CmA, when reaching 4～4.3V, terminal voltage carries out constant-potential charge with this voltage, finished the operation of charging for the first time in 3～30 minutes later on, and the current value of the battery when measuring above-mentioned constant-potential charge and/or the temperature of the battery in the charging operation, judge the bad of battery
After the operation of charging for the first time, carry out the timeliness operation,
Then, carry out the constant current charge of 0.2CmA, carry out constant-potential charge with this voltage when terminal voltage reaches 4.2V, finish the operation of charging for the second time when current value reaches 0.05CmA.
2. the manufacture method of a secondary cell is characterized in that,
Secondary cell for assembling, above-mentioned secondary cell is by constituting with the lower part: positive pole comprises and can absorb the lithium transition-metal oxide of emitting lithium ion; Negative pole comprises and can absorb the material with carbon element of emitting lithium ion; Division board is separated above-mentioned positive pole and negative pole, is made of megohmite insulant; And the electrolyte that comprises lithium salts,
After secondary cell for assembling, carry out the constant current charge of 5～20CmA, when reaching 4～4.3V, terminal voltage carries out constant-potential charge with this voltage, finished the operation of charging for the first time in 3～30 minutes later on,
After the operation of charging for the first time, carry out the timeliness operation, and, judge the bad of battery by being determined at the magnitude of voltage that carries out the battery in the timeliness operation,
Then, carry out the constant current charge of 0.2CmA, carry out constant-potential charge with this voltage when terminal voltage reaches 4.2V, finish the operation of charging for the second time when current value reaches 0.05CmA.
3. the manufacture method of secondary cell according to claim 1 and 2 is characterized in that, the constant current charge first time in the operation of charging in 30～70% scopes of the rated capacity of battery.
4. the manufacture method of secondary cell according to claim 1 and 2 is characterized in that, more than 3 minutes below 30 minutes in the time, and the constant current charge first time in the operation of only once charging.
5. the manufacture method of secondary cell according to claim 1 and 2 is characterized in that, is carrying out constant-potential charge more than 3 minutes below 20 minutes in the time.
6. the manufacture method of secondary cell according to claim 1 is characterized in that, in the charging operation, according to the current attenuation amount of the unit interval after the current potential arrival regulation current potential, judges the bad of battery.
7. the manufacture method of secondary cell according to claim 6 is characterized in that, judges that attenuation is that positive battery is bad.
8. the manufacture method of secondary cell according to claim 1 is characterized in that, the battery that the temperature of the battery in the judgement charging operation becomes more than 40 ℃ is bad.
9. the manufacture method of secondary cell according to claim 1 is characterized in that, the variations in temperature of judging the unit interval in the charging operation occur secondary above on the occasion of battery be bad.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP019008/2003 | 2003-01-28 | ||
| JP2003019017A JP4358526B2 (en) | 2003-01-28 | 2003-01-28 | Manufacturing method of secondary battery |
| JP2003019008A JP2004234896A (en) | 2003-01-28 | 2003-01-28 | Inspection method of secondary battery |
| JP019017/2003 | 2003-01-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1518154A CN1518154A (en) | 2004-08-04 |
| CN100416908C true CN100416908C (en) | 2008-09-03 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2004100014157A Expired - Fee Related CN100416908C (en) | 2003-01-28 | 2004-01-07 | Manufacturing method of secondary battery |
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| CN (1) | CN100416908C (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323076A (en) * | 2000-05-16 | 2001-11-21 | 索尼株式会社 | Charging method for nonaqueous electrolyte secondary battery |
| CN1340874A (en) * | 2000-05-23 | 2002-03-20 | 佳能株式会社 | Detecting method for internal state of rechargeable battery, device and equipment with said device |
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2004
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323076A (en) * | 2000-05-16 | 2001-11-21 | 索尼株式会社 | Charging method for nonaqueous electrolyte secondary battery |
| CN1340874A (en) * | 2000-05-23 | 2002-03-20 | 佳能株式会社 | Detecting method for internal state of rechargeable battery, device and equipment with said device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1518154A (en) | 2004-08-04 |
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